The oxidative dehydrogenation of butane on a V/MgO doped catalyst has been studied under anaerobic conditions. Fe, Co and Mo were used as dopants with atomic ratios to V of 1:20 and 1:100. Under these conditions, the oxygen from the catalyst lattice is consumed by the reaction and the degree of solid oxidation changes during the process. A kinetic model is applied in which the relation between the reaction rates and the degree of catalyst oxidation is taken into account. The V/MgO-Fe (1%) is the most promising doped catalyst for increasing the yield to butenes + butadiene. The effect of the doping in the kinetic scheme supposes an increase in the butane oxidation constant to COx, and a decrease in the formation of butadiene from butane and in the deep oxidation of butadiene. The final effect is an improvement in the selectivity to butenes + butadiene. (C) 2004 Elsevier B.V. All rights reserved.